Process for producing hydrogenated amorphous silicon film

ABSTRACT

A process for production of a hydrogenated amorphous silicon film of a silicon compound containing at least one element selected from the group consisting of hydrogen and halogens and having a photosensitivity of not less than 0.1 erg/cm 2  at 780 nm, which comprises 
     supplying a gas selected from the group consisting of SiH 4 , SiF 4  and Si 2  H 6  into a discharge space, and 
     subjecting the gas to glow discharge within the discharge space having a gradient discharge intensity. 
     The present invention provides an a-SiH film which has a remarkable high sensitivity in a long wavelength region with maintaining a high photosensitivity in a visible light region, and has a remarkable less defect density, and the process for production of such film in a high deposition rate.

This application is a division of Ser. No. 870,035, filed June 3, 1986now abandoned.

FIELD OF THE INVENTION

This invention relates to a hydrogenated amorphous silicon film(hereinafter, expressed as "a-SiH") which has a high photosensitivity ata long wavelength region and over a wide range of wavelengths withoutcontaining metals (impurity) such as germanium, tin and the like.

BACKGROUND OF THE INVENTION

Recently, an a-SiH film is in a development stage for a wide practicalapplication such as a solar cell, an optical sensor, a field effecttransistor (FET), an electrophotographic photoreceptor and etc, and is aremarkable material for electronics industry.

As methods for producing such a-SiH, there are known methds that asilicon target is sputtered in an atmosphere of active hydrogen, andthat SiH₄ or SiF₄ gas is decomposed by glow discharging.

By sputtering method, there can be hardly obtained an a-SiH film havinggood characteristics because it is difficult to control a hydrogencontent which have significant effects upon film characteristics of ana-SiH.

On the other hand, by glow discharging method, there can be obtained afilm having less defects such as dangling bond, void, or the like. Theglow discharging method also has a merit that control of valenceelectrons for n or p type a-SiH is possible, and that a film can beformed onto an appropriate shape of a substrate (i.e. a film having awide area can be obtained). Therefore, recently, an a-SiH film havinggood characteristics is mainly produced by glow discharging method.

However, an a-SiH film produced by the conventional glow dischargingmethod has an insufficient photosensitivity region, particularly at along wavelength of longer than 700 nm. Therefore, for example, when sucha film is an image pickup element, the film can not cover all regions ofvisible rays to pickup an image. When a film is used for a solar cell,such a film can not cover a long wavelength region of a sunlight. Itinduces a disadvantage that a sufficient cell efficiency can not beobtained because a light having a long wavelength region is notutilized. Further, when such a film is used for a electrophotograhicphotoreceptor, there are defects such as limitation of colors to beused, and the like. Moreover, when such a film is used for aphotoreceptor in a semiconductor laser printer having a light source ofsemiconductor laser, it also has an insufficient photosensitivity for apractical use. Thus, an a-SiH film for a optical functional device hasbeen insufficient in optical characteristics.

Then, there has been hitherto produced a silicon alloy containing metalsusch as germanium, tin and the like as an impurity in order to promotethe absorption of a light having a low energy and to provide aphotosensitivity having a long wavelength by making a band gap energynarrow. The introduction of such metals, however, makes disorder of ana-SiH structure itself and involves a defect of remarkable increase of adefect level. For example, when an a-SiH film is used as aphotoreceptor, the increase of a defect level in an a-SiH film causesresidual voltage to make a trouble of so called "memory, ghost image",so that it injuries a commercial value of an a-SiH film.

The above glow discharge method has a further problem to be solved, thatis, for example, it has a low deposition rate or low forming rate of afilm. The conventional glow discharge method only achieves 1-2 μ/hr atmaximum.

OBJECT OF THE INVENTION

The present invention have intensively studied a novel glow dischargemethod for providing an a-SiH film with a wide region ofphotosensitivity without containing the other metals, or for providingit with a high photosensitivity at a long wavelength region withmaintaining a high sensitivity to visible rays. As the result, it hasbeen found that a specific apparatus and specific conditions inproduction, particularly distributing the grade of a plasma intensity ofa glow discharging space can provide an a-SiH film having goodcharacteristics in a high deposition rate.

An object of the present invention is to provide an a-SiH film which hasa remarkable high sensitivity at a long wavelength region withmaintaining a high photosensitivity in a visible light region, and has aremarkable less defect density.

Further object of the present invention is to provide a process forproduction of the above a-SiH film in a high deposition rate.

These and other objects and advantages of the present invention will beapparent to those skilled in the art from the following description.

SUMMARY OF THE INVENTION

The present invention provides an a-SiH film having a highphotosensitivity at a long wavelength region which comprises a siliconcompound containing at least one element selected from the groupconsisting of hydrogen and halogens, and said amorphous silicon filmhaving a photo-sensitivity of not less than 0.1 cm2/erg at 780 nm.

The present invention also provides a method for production of an a-SiHfilm of a silicon compound containing at least one element selected fromthe group consisting of hydrogen and halogens which comprises:

supplying a gas selected from the group consisting of SiH₄, SiF₄ and Si₂H₆ into a discharge space, and

subjecting the gas to flow discharge within the discharge space having agradient discharge intensity.

The photosensitivity herein was measured in the following method.

A sample for measurement was produced by forming a block layer (a "ptype" a-SiH film for a positive charge and a "n type" a-SiH film for anegative charge) onto an aluminium substrate depositing an a-SiH film tobe evaluated (a-SiH film of the present invention) onto the block layer,and further forming a protective layer over the a-SiH film. Theresulting sample was treated with corona discharge treatment by a highvoltage continuous current (6-8 KV) to give a surface charge onto thea-SiH sample. Then, the sample was irradiated with a monochromatic light(0.66 μW/cm²) having a constant light energy. The surface chargeproduced above was disappeared by the irradiation of a monochromaticlight. The photosensitivity is defined as a reciprocal of an energyamount of a light which is required for decreasing a surface charge intoa half.

The a-SiH film of the present invention preferably has a remarkable lessdefect density as described above. By measurement with DLTS (Deep LevelTransient Spectroscopy) method, a conventional a-SiH film has alocalized density of state of 1×10¹⁶ to 5×10¹⁶ cm⁻³ eV⁻¹, but the a-SiHfilm of the present invention has a decreased defect level of 4×10¹⁴ to6×10¹⁴ cm⁻³ eV⁻¹. Such structural defect has significant effects uponnot only an application of an a-SiH film but also all applications ofgeneral semiconductive materials, so that the decreasing a defectdensity has been a remarkable important subject in development of suchmaterials.

Particularly, when an a-SiH film is used as an electrophotographicphotoreceptor or a photoconductive layer of a photoreceptor for a laserprinter, a high defect density thereof undesirably increases a residualvoltage based on a carrier trap, makes a image-flow and decreases aneffective copy speed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 to 3 are schematic cross-section views of apparatus used inproducing the a-SiH film of the present invention.

FIG. 4 is a graph showing spectral response characteristics of a-SiHfilm (photoconductive layers).

FIG. 5 is a schematic cross-section view of apparatus used in aconventional a-SiH film.

DETAILED DESCRIPTION OF THE INVENTION

The process for production of the a-SiH film of the present invention isillustrated by using the accompany drawings.

FIG. 1 shows a capacitively coupled glow discharge apparatus for formingan a-SiH film on a substrate with distributing a gradient of dischargeintensity by dividing a discharge space into two parts.

After a reaction chamber 8 is degassed until about 10⁻⁶ torr, into whicha silicon composition 9 (raw gas) containing at least hydrogen andhalogens is charged. The raw gas 9 may be SiH₄, SiF₄, Si₂ H₆ or the likemixed with optional dope gases such as B₂ H₆, H₂, He, Ar or the like asa dilient gas, which controls the characteristics of a semiconductor.The raw gas 9 is passed through a discharge space to deposit it onto asubstrate 5. In the discharge space, there is provided an additionalelectrode 2 having apertures between electrodes 1 and 4 to divide thedischarge space into two parts, which are consisting of a dischargespace (W) between electrodes 1 and 2, and other discharge space (S)between electrodes 2 and 4. The discharge space is divided by one RFsource (high-frequency source) 6 to cause a weak discharge in thedischarge space (W) and a strong discharge in the discharge space (S).

The raw gas material is exposed to steps of decomposition, excitationand diffusion thereof and reaction on the surface during passing fromthe weak discharge section to the strong discharge section, after whichit is deposited onto the surface of the substrate.

The distribution of a discharge intensity in the process of the presentinvention is further illustrated. The distribution of a dischargeintensity is evaluated by measuring an emission spectrum from a glowdischarge plasma of a raw gas with an apparatus for optical emissionspectrpscopy (OES). Such OES provides a convenient means forin-process-monitoring during the growth of a film in a plasma since theintensity of an emission on each wavelength sensitively varies withdischarge pressure, concentration of a raw material, RF power, flow rateof a gas, kind of a dope gas, external magnetic field. A dischargeintensity during the production of a film is evaluated by measuring aplasma emission, which is conducted from each divided plasma chambersthrough a peephole thereof, condensed by a condenser adaptor, andconducted to a spectroscope through an optical fiber for spectrumanalysis before amplification. When hydrogenated silicon such as SiH₄ isused as a raw material, the intensity of discharge is evaluated by theobservation of an emission intensity of SiH having a wavelength of 414nm, which is a most significant emission species for a rate of theproduction of a film and the characteristics of a film. When halogenatedsilicon such as SiF₄ is used as a raw material, the intensity ofdischarge is evaluated by the observation of an emission intensity ofSiF having a most significant emission species of 440 nm. Thus, a properdischarge intensity can be set up according to desired physicalproperties of a film.

In FIG. 1, it is essential to use electrodes having air-permeableapertures as electrodes 1 and/or 2. There is preferably used, forexample, various kinds of meshes, a punching metal or the like. The sizeof the air-permeable aperture in the electrode has a remarkablysignificant effects upon the number of defects and a photosensitivity ofthe film.

That is, there is a suitable range of a size of producing an a-SiH filmhaving a photosensitivity of over 0.1 cm2/erg at a long wavelengthregion, for example, at 780 nm while maintaining a less defect numberand a high sensitivity to a visible light region.

In case of a wire netting, it has preferably an aperture size of 0.5 to100 mesh, more preferably 1 to 30 mesh. When the aperture size is over100 mesh, it maintains a relative high photosensitivity, but itundesirably causes some decrease of a photosensitivity at a longwavelength region. On the other hand, when smaller than 0.5 mesh, itmaintains a relative high photosensitivity at a long wavelength region,but it undesirably induces a decrease of sensitivity to a visible lightregion. The mesh indicating a size of an aperture of a wire netting isherein defined as follows for convenience. That is, "mesh" indicates thenumber of holes per one inch length. Then, when a size of a hole is 1inch, an electrode is designated an electrode having an aperture size of1 mesh. When a size of a hole is 2 inches, an electrode is designated anelectrode having an aperture size of 0.5 mesh.

As to the conditions for production, the temperature of a substrate alsohave significant effects upon the photosensitivity. Although thephotosensitivity relatively increases at a long wavelength withincreasing the temperature of the substrate, a charging ability of aphotoconductive layer is decreased. Therefore, when the film is used asa photoconductive layer for a electrophotographic photoreceptor or aphotoreceptor in a laser printer, the temperature of the substrate ispreferably not more than 350° C. Although, the temperature of thesubstrate which produces the minimim defect density is varied dependingon the size of the aperture of the electrodes which divide the dischargespace, the temperature is preferably from 230°-315° C. when theelectrode has an aperture size of 1-100 mesh.

The present invention has an essential feature that a plasma space isdivided into a multistage for the production of an a-SiH film in glowdischarge method.

Although FIG. 1 shows a discharge space divided into two spaces, thedischarge space used in the present invention may be divided into anynumbers of spaces provided that it gives the gradient of a plasmaintensity, and the number of division in not limited. Such division iscarried out by appropriately using RF and/or DC source as a powersource.

FIG. 2 shows a further embodiment of the present invention wherein thea-SiH film is formed by inducing DC discharge between electrodes 1 and2, and RF discharging between electrodes 3 and 4. The space between theelectrodes 1 and 2 is provided with a weak discharge intensity (W), andthe space between electrodes 3 and 4 is provided with a strong dischargeintensity.

FIG. 3 shows an other embodiment of the present invention wherein thedischarge space is divided with two RF power sources. The space betweenthe electrodes 1 and 2 is provided with a weak discharge intensity (W),and the space between electrodes 3 and 4 is provided with a strongdischarge (S).

Either apparatus of FIG. 2 or FIG. 3 can produce the a-SiH film of thepresent invention. Althought it is not unclear why the method canproduces the a-SiH film having a wide phtosensitivity region, there canbe clearly found out that such method results in a smaller optical bandgap energy (Eg opt) rather than that of a conventional a-SiH. Aconventional a-SiH film usually has a Eg opt of about 1.7 eV. On theother hand, under an appropriate condition, the present invention canprovide the a-SiH film which has a narrow Eg opt of about 1.58 to 1.61eV as a sole a-SiH film. It seems that the absorption of a low energylight or a light having a long wave length region based on the abovenarrow Eg opt causes the increased photosensitivity having a longwavelength.

Advantages of the Invention

The a-SiH film of the present invention, which differs from aconventional a-SiH film, has a higher photosensitivity at a longwavelength region or at 780 nm without containing metal impurity such asgermanium, tin etc, so that it can be preferably used for aphotoconductive material of an electrophotographic photoreceptor as wellas a photoreceptor of a semiconductor laser.

The present invention is further illustrated by the following Examples,but not intended to limit thereto.

EXAMPLE 1

Referring FIG. 1, either electrode 1 or 2 had a size of apertures of 10mesh, and they were disposed at a distance of 25 mm apart from eachother. An electrode 4 was disposed at a distance of 25 mm apart fromelectrode 2. On electrode 4, a polished A1 plate was disposed. Therewere caused a weak discharge section between electrodes 1 and 2, and astrong discharge section between the electrodes 2 and 4 with applying anelectric power of 200 W by RF power source 6 (13.56 MHz) at a substancetemperature of 240° C.

The samples of a photoreceptor having three layers, which were used forevaluation, were obtained with the above apparatus under the conditionsshown in Table 1. That is, the sample had a blocking layer, aphotoconductive layer and a surface layer on A1 plate in order. In suchproduction of the film, there was obtained a deposition rate of aphotoconductive layer of 25 μ/hr. Using the resultant samples of thephotoreceptor having three layers, a saturation charge ability and aspectral response at a wavelength of 400-800 nm and a light intensity of0.66 μW/cm² were measured. The results are shown in Table 2 and FIG. 4.Using the sample obtained from the same method described above, alocalized density of state in an energy gap of the sample was measurizedby DLTS method. The result is shown in Table 2.

EXAMPLE 2

A sample having three layers was obtained in the same manner asdescribed in Example 1 shown in Table 1 except for using of metalnetting electrodes of 50 mesh (see Table 1). The deposition rate of aphotoconductive layer was 23 μ/hr. The resultant sample was used for themeasurement of a spectral response, a saturation charge acceptance and alocalized density of state. The results are shown in FIG. 4 and Table 2.

EXAMPLE 3

A sample having three layers was obtained in the same manner asdescribed in Example 1 shown in Table 1 except for using of a substratetemperature of 320° C. The deposition rate of a photoconductive layerwas 20 μ/hr. The resultant sample was used for the measurement of aspectral response, a saturation discharge ability and a localizeddensity of state. The results are shown in FIG. 4 and Table 2.

EXAMPLE 4

An a-SiH film was obtained with the apparatus shown in FIG. 3, whereinthe discharge space was divided by two high-frequency power sources 6.Referring FIG. 3, either electrode 1, 2 or 3 was a metal nettingelectrode having a size of apertures of 10 mesh. The distance betweenelectrodes 1 and 2 was 25 mm, the distance between electrodes 3 and 4was also 25 mm, and the distance between electrodes 2 and 3 was 3 mm.The temperature of a substrate 5 was 270° C. The sampel having threelayers was obtained by applying an electric power of 20 W betweenelectrodes 1 and 2, and an electric power of 200 W between electrodes 3and 4, with using a raw gas having a composition shown in Table 1. Thedepositoin rate of a photoconductive layer was 21 μ/hr.

The resultant sample was used for the measurement of a spectralresponse, a saturation discharge ability and a localized density ofstate. The results are shown in FIG. 4 and Table 2.

EXAMPLE 5

Using SiF₄ gas as a raw material for an a-SiH film a photoreceptorsample having three layers was obtained in a same manner as described inExample 4. The deposition rate of a photoconductive layer was 28 μ/hrThe characteristics of the resultant film was evaluated. The results areshown in FIG. 4 and Table 2.

EXAMPLE 6

As shown in FIG. 2, an a-SiH film was formed with an apparatus havingthe divided discharge spaces whcih consists of a space defined byelectrodes 1 and 2 with DC power source and a space defined byelectrodes 3 and 4 with RF power source 6. Either electrode 1, 2 or 3was a metal netting electrode having a size of apertures of 5 mesh. Thetemperature of a substrate 5 was 300° C. Either distance betweenelectrodes 1 and 2 or electrodes 3 and 4 was 25 mm, and the distancebetween electrodes 2 and 3 was 3 mm. The sample of a photoreceptorhaving three layers was obtained by applying an electric power of 15 Wbetween electrodes 1 and 2, and an electric power of 300 W betweenelectrodes 3 and 4, with using a raw gas having a composition shown inTable 1. The deposition rate of a photoconductive layer was 22 μ/hr.

The characteristics of the resultant sample were evaluated. The resultsare shown in FIG. 4 and Table 2.

REFERENCE EXAMPLE 1

An a-SiH was obtained with a conventional glow discharge apparatushaving parallel round plate type electrodes without divided dischargespaces shown in FIG. 5. Each round electrodes had a diameter of 10 cm,and was disposed at a distance of 4 cm apart from each other. Thetemperature of a substrate was 250° C. The sample having three layerswas obtained by applying high-frequency voltage of 13.56 MHz under anelectric power of 15 W onto the electrodes, with using a raw gas havinga composition shown in Table 1. The deposition rate of a photoconductivelayer was 3.5 μ/hr. The characteristics of the resultant film wereevaluated. The results are shown in FIG. 4 and Table 2.

                                      TABLE 1                                     __________________________________________________________________________                           Photoconductive.sup.1                                  Blocking Layer         Layer    Surface Layer                                 __________________________________________________________________________    Ex. 1 SiH.sub.4  200 cc/min                                                                          SiH.sub.4                                                                        200 cc/min                                                                          SiH.sub.4                                                                        200 cc/min                                       B.sub.2 H.sub.6 /H.sub.2 (5000 ppm)                                                      20             N.sub.2                                                                          60                                         2     SiH.sub.4  200 cc/min                                                                          SiH.sub.4                                                                        200 cc/min                                                                          SiH.sub.4                                                                        200 cc/min                                       B.sub.2 H.sub.6 /H.sub.2 (5000 ppm)                                                      20             N.sub.2                                                                          60                                         3     SiH.sub.4  200 cc/min                                                                          SiH.sub.4                                                                        200 cc/min                                                                          SiH.sub.4                                                                        200 cc/min                                       B.sub.2 H.sub.6 /H.sub.2 (5000 ppm)                                                      20             N.sub.2                                                                          60                                         4     SiH.sub.4  300 cc/min                                                                          SiH.sub.4                                                                        300 cc/min                                                                          SiH.sub.4                                                                        300 cc/min                                       B.sub.2 H.sub.6 /H.sub.2 (5000 ppm)                                                      30             N.sub.2                                                                          90                                         5     SiF.sub.4  150 cc/min                                                                          SiF.sub.4                                                                        150 cc/min                                                                          SiH.sub.4                                                                        150 cc/min                                       B.sub.2 H.sub.6 /H.sub.2 (5000 ppm)                                                      15             N.sub.2                                                                          45                                         6     SiH.sub.4  150 cc/min                                                                          SiH.sub.4                                                                        150 cc/min                                                                          SiH.sub.4                                                                        150 cc/min                                       B.sub.2 H.sub.6 /H.sub.2 (5000 ppm)                                                      15             N.sub.2                                                                          45                                         Ref. Ex. 1                                                                          SiH.sub.4  20 cc/min                                                                           SiH.sub.4                                                                        20 cc/min                                                                           SiH.sub.4                                                                        20 cc/min                                        B.sub.2 H.sub.6 /H.sub.2 (5000 ppm)                                                      2              N.sub.2                                                                          6                                          __________________________________________________________________________     .sup.1 Photoconductive layer corresponds to the aSiH film of the present      invention.                                                               

                  TABLE 2                                                         ______________________________________                                                 Saturation Charge                                                                        Localized Density of                                               Acceptance.sup.2                                                                         State                                                              (V/μm)  (cm.sup.-3 eV.sup.-1)                                     ______________________________________                                        Ex. 1      29           3 × 10.sup.15                                   2          24           2 × 10.sup.15                                   3          13           5 × 10.sup.14                                   4          22           1 × 10.sup.15                                   5          21           4 × 10.sup.14                                   6          17           6 × 10.sup.14                                   Ref. Ex. 1 20           3 × 10.sup.16                                   ______________________________________                                         .sup.2 Saturation charge acceptance:                                     

An a-SiH sample was treated with corona discharge treatment under a highvoltage of 6.5 KV to give the sample a surface charge. The dischargetreatment was repeated to saturate the amount of the surface charge,which was measured with a surface electrometer.

What is claimed is:
 1. A process for production of a hydrogenatedamorphous silicon film of a silicon compound containing at least oneelement selected from the group consisting of hydrogen and halogenswhich comprises:supplying a gas selected from the group consisting ofSiH₄, SiF₄ and Si₂ H₆ into a discharge space which is divided intoplural parts having different discharge intensities to give a gradientof discharge intensity to that the strongest discharge intensity ispresent in the part facing a substrate on which the gas is deposited,and subjecting the gas to flow discharge within the discharge space. 2.A process accordng to claim 1, wherein a raw gas is passed from a partof the space having a low discharge intensity into a part of the spacehaving a high discharge intensity.